Compositions for dyeing keratinous fibers comprising pyrazoloazoles; their use in dyeing as oxidation base and dyeing process; and novel pyrazoloazoles

Abstract

A composition for dyeing keratinous fibers, in particular human keratinous fibers, such as human hair, containing, in a medium suitable for dyeing:as oxidation base, at least one compound of formula (I) below:in which:R1 is a hydrogen atom, an alkyl radical, an aryl radical, a heterocycle radical, or a halogen atom,R2 is a hydrogen atom, an alkyl radical, a hydroxyalkyl radical, or an aminoalkyl radical,Za, Zb and Zc are independently a nitrogen atom or a carbon carrying an R3 or R4 radical with meanings identical to those of R1; wherein at least one of Za, Zb and Zc is a nitrogen atom; it being possible for R3 and R4 to form between themselves a substituted or unsubstituted aromatic ring.

What is claimed is:  
     
       1. A composition for the oxidation dyeing of keratinous fibers, wherein said composition comprises, in a medium suitable for dyeing: 
       as oxidation base, at least one pyrazoloazole compound of formula (I) or at least one acid addition salt thereof:                    
       in which: 
       R 1  represents: a hydrogen atom; a linear or branched C 1 -C 20  alkyl radical, optionally substituted by 1 or 2 radicals R chosen from a halogen atom, a C 1 -C 4  alkyl radical, a trifluoromethyl radical, a carboxyl radical, an alkyldioxy radical, a nitro radical, a cyano radical, a hydroxyl radical, an alkoxy radical, an aryloxy radical, an amino radical, an alkylamino radical, an acylamino radical, a carbamoyl radical, a sulphonamido radical, a sulphamoyl radical, an imido radical, an alkylthio radical, an arylthio radical, an aryl radical, a (C 1 -C 4 )alkoxy-carbonyl radical and an acyl radical; an aryl radical optionally substituted by 1 or 2 radicals R as defined above; a 5- or 6-membered heterocycle containing at least one nitrogen, oxygen or sulphur atom wherein said heterocycle is optionally substituted by 1 or 2 radicals R as defined above;  
       when R 1  denotes a C 1 -C 4  alkyl radical, an aryl radical or a 5- or 6-membered heterocycle, it can be connected to the carbon atom of the pyrazole via an oxygen, nitrogen or sulphur atom;  
       R 1  can, additionally, denote a halogen atom; a trifluoromethyl radical; a 4-trifluoromethylphenyl ring: a C 1 -C 4  monohydroxyalkyl radical; a C 1 -C 4  aminoalkyl radical; a (C 1 -C 4 )alkylamino(C 1 -C 4 )alkyl radical; a C 1 -C 4  alkoxy radical; an aryloxy radical; a C 1 -C 4  alkylthio radical; an arylthio radical; a C 1 -C 4  alkylsulphonyl radical; an acyl radical; a sulphonyl radical; a sulphinyl radical; a phosphonyl radical; a carbamoyl radical; a sulphamoyl radical; a cyano radical; a siloxy radical; an amino radical; an acylamino radical; an acyloxy radical; a carbamoyloxy radical; a sulphonamide radical; an imide radical; a ureido radical; a sulphamoylamino radical; a (C 1 -C 4 )alkoxy-carbonylamino radical; an aryloxycarbonylamino radical; a (C 1 -C 4 )alkoxy-carbonyl radical; an aryloxycarbonyl radical; a carboxyl radical; or a hydroxyl radical;  
       R 2  is a hydrogen atom; a C 1 -C 4  alkyl radical; a C 1 -C 4  monohydroxyalkyl radical; a C 2 -C 4  polyhydroxyalkyl radical; a C 1 -C 4  aminoalkyl radical; a (CH 2 ) p —X—(CH 2 ) q OR′ radical in which p and q are identical or different integers ranging from 1 to 3, R′ represents a hydrogen atom or a methyl radical, and X denotes an oxygen atom or an NR″ group in which R″ represents a hydrogen atom or a methyl radical; a (C 1 -C 4 )alkoxy(C 2 -C 4 )alkyl radical; or a di(C 1 -C 4 )alkylamino(C 1 -C 4 )alkyl radical;  
       Z a , Z b  and Z c  represent, independently of one another, a nitrogen atom or a carbon atom carrying an R 3  or R 4  radical, where R 3  and R 4  independently have the same meanings as those indicated above for R 1 , with the proviso that at least one of the Z a , Z b  and Z c  radicals is other than a carbon atom; R 3  and R 4  can also together form a substituted or unsubstituted aromatic ring.  
     
     
       2. A composition according to  claim 1 , wherein said keratinous fibers are human keratinous fibers. 
     
     
       3. A composition according to  claim 2 , wherein said human keratinous fibers are hair. 
     
     
       4. A composition according to  claim 1 , wherein, when R 1  represents a linear or branched C 1 -C 20  alkyl radical substituted by one or two radicals R wherein R is an aryl radical or when R 1  is an aryl radical, said aryl radical is phenyl or naphthyl. 
     
     
       5. A composition according to  claim 1 , wherein R 1  represents a 5 or 6 membered heterocycle containing at least one nitrogen, oxygen or sulphur atom and wherein said heterocycle is pyridyl, quinolyl, pyrrolyl, morpholyl, furanyl, tetrahydorfuranyl, pyrazolyl, triazolyl, thiazolyl, oxazolyl, imidazolyl or thiadiazolyl. 
     
     
       6. A composition according to  claim 1 , wherein R 1  is a halogen atom and wherein said halogen is bromine, chlorine, or fluorine. 
     
     
       7. A composition according to  claim 1 , wherein R 1  is a hydrogen atom; a linear or branched C 1 -C 4  alkyl radical; a phenyl ring; a phenyl ring substituted by a halogen atom, a C 1 -C 4  alkyl radical, a C 1 -C 4  alkoxy radical, a nitro radical, an amino radical, a trifluoromethyl radical or by a C 1 -C 4  alkylamino radical; a benzyl radical; a benzyl radical substituted by a halogen atom, a C 1 -C 4  alkyl radical, a C 1 -C 4  alkoxy radical, a nitro radical, an amino radical, a trifluoromethyl radical or by a C 1 -C 4  alkylamino radical; a heterocycle chosen from thiophene, furan or pyridine rings; a trifluoromethyl radical; a (CH 2 ) p —X—(CH 2 ) q —OR′ radical in which p and q are identical or different integers ranging from 1 to 3, R′ represents a hydrogen atom or a methyl radical and X denotes an oxygen atom or an NR″ radical in which R″ denotes a hydrogen atom or a methyl radical; a C 1 -C 4  hydroxyalkyl radical; a C 1 -C 4  aminoalkyl radical; a C 1 -C 4  alkylamino radical; a di(C 1 -C 4 )alkylamino radical; an arylamino radical; an alkoxy radical chosen from methoxy, ethoxy and phenoxy; a halogen atom chosen from bromine, chlorine and fluorine; a carboxyl radical; a C 1 -C 4  alkoxycarbonyl radical; a phenyloxycarbonyl radical; a methylthio radical; an ethylthio radical; a phenylthio radical; a methanesulphonyl radical; a cyano radical; an amino radical; or a hydroxyl radical. 
     
     
       8. A composition according to  claim 7 , wherein R 1  is a hydrogen atom; an alkyl radical chosen from methyl, ethyl, isopropyl and tert-butyl radicals; a halogen atom chosen from chlorine and fluorine; a phenyl radical; a toluyl radical; a 4-chlorophenyl radical; a 4-methoxyphenyl radical; a 3-methoxyphenyl radical; a 2-methoxyphenyl radical; a benzyl radical; a heterocycle chosen from pyridyl, furyl and thienyl rings; a trifluoromethyl radical, a hydroxymethyl radical; an aminomethyl radical; a methoxy radical; an ethoxy radical; a methylamino radical; an ethylamino radical; a dimethylamino radical; a carboxyl radical; a methoxycarbonyl radical; an ethoxycarbonyl radical or a cyano radical. 
     
     
       9. A composition according to  claim 8 , wherein R 1  is a hydrogen atom; a chlorine atom; a methyl radical; an ethyl radical; a phenyl radical; a toluyl radical; a 4-chlorophenyl radical; a 4-methoxyphenyl radical; a benzyl radical; a trifluoromethyl radical; a methoxy radical; an ethoxy radical; a carboxyl radical; a methylamino radical; a dimethylamino radical or a cyano radical. 
     
     
       10. A composition according to  claim 1 , wherein R 2  is a hydrogen atom; a methyl radical or a β-hydroxyethyl radical. 
     
     
       11. A composition according to  claim 10 , wherein R 2  is a hydrogen atom. 
     
     
       12. A composition according to  claim 1 , wherein R 3  and R 4  are independently a hydrogen atom; a hydroxyl radical; an amino radical; a linear or branched C 1 -C 4  alkyl radical; a trifluoromethyl radical; a phenyl ring; a phenyl ring substituted by one or two radicals R chosen from a halogen atom, a C 1 -C 4  alkyl radical, a C 1 -C 4  alkoxy radical, a hydroxyl radical, a carboxyl radical, a nitro radical, a C 1 -C 4  alkylthio radical, a methylenedioxy radical, an amino radical, a trifluoromethyl radical and a C 1 -C 4  alkylamino radical; a benzyl radical; a benzyl radical substituted by a halogen atom, a methyl or isopropyl radical or a methoxy radical; a C 1 -C 4  monohydroxyalkyl radical; a C 1 -C 4  aminoalkyl radical; a (C 1 -C 4 )alkylamino(C 1 -C 4 )alkyl radical; an alkoxy radical chosen from methoxy and ethoxy radicals; a phenoxy radical; a methylthio radical; an ethylthio radical; a phenylthio radical; a methanesulphonyl radical; or a substituted or unsubstituted aromatic ring formed jointly by R 3  and R 4 . 
     
     
       13. A composition according to  claim 12 , wherein R 3  and R 4  jointly form a substituted or unsubstituted aromatic ring, said ring being a phenyl ring, pyridyl ring or phenyl ring substituted by a sulphonyl radical, a halogen atom, a C 1 -C 4  alkoxy radical, a C 1 -C 4  alkyl radical, a nitro radical, a cyano radical, an amino radical, a C 1 -C 4  alkylamino radical or a trifluoromethyl radical. 
     
     
       14. A composition according to  claim 12 , wherein R 3  and R 4  are independently a hydrogen atom; an alkyl radical chosen from methyl, ethyl, isopropyl, n-proply and tert-butyl radicals; a phenyl ring; a toluyl ring; a 2-, 3- or 4-chlorophenyl ring; a 3- or 4-hydroxyphenyl ring; a 3- or 4-aminophenyl ring; a 3- or 4-methoxyphenyl ring; a 4-trifluoromethylphenyl ring; a benzyl ring; a trifluoromethyl radical; a hydroxymethyl radical; a hydroxyethyl radical; a hydroxyisopropyl radical; an aminomethyl or aminoethyl radical; a methoxy or ethoxy radical; a methylthio or ethylthio radical; or a substituted or unsubstituted aromatic ring formed jointly by R 3  and R 4 . 
     
     
       15. A composition according to  claim 14 , wherein R 3  and R 4  jointly form a substituted or unsubstituted aromatic ring, said ring being a phenyl, toluyl, sulphonylphenyl or chlorophenyl ring. 
     
     
       16. A composition according to  claim 14 , wherein R 3  and R 4  independently are a hydrogen atom; a methyl radical; an ethyl radical; an isopropyl radical; a phenyl ring; a 4-chlorophenyl ring; a 4-methoxyphenyl ring; a 4-aminophenyl ring; a methoxy or ethoxy radical; a methylthio or ethylthio radical; or R 3  and R 4  jointly form a phenyl ring. 
     
     
       17. A composition according to  claim 1 , wherein said at least one compound of formula (I) is chosen from: 
       i) pyrazolo[1,5-b]-1,2,4-triazoles of formula (Ia) and the acid addition salts thereof:                    
       ii) pyrazolo[3,2-c]-1,2,4-triazoles of formula (Ib) and the acid addition salts thereof:                    
       iii) pyrazolotetrazoles of formula (Ic) and the acid addition salts thereof:                    
       iv) pyrazolo[1,5-a]imidazoles of formula (Id) and the acid addition salts thereof:                    
       v) pyrazolo[5,1-e]pyrazoles of formula (Ie) and the acid addition salts thereof:                    
       vi) pyrazolo[5,1-e]-1,2,3-triazoles of formula (If) and the acid addition salts thereof:                    
       in which R 1 , R 2 , R 3  and R 4  have the same meanings as those indicated in  claim 1 . 
     
     
       18. A composition according to  claim 17 , wherein said pyrazolo[1,5-b]-1,2,4-triazoles of formula (Ia) or said pyrazolo[3,2-c]-1,2,4-triazoles of formula (Ib) are chosen from those compounds in which: 
       R 1  is a hydrogen atom or a methyl, trifluoromethyl, carboxyl, phenyl, ethoxy, cyano, ethylthio, amino or hydroxyl radical;  
       R 2  is a hydrogen atom; and  
       R 3  is a hydrogen atom or a methyl, β-aminoethyl, ethyl, isopropyl, phenyl, β-hydroxyethyl, methylthio or ethoxy radical.  
     
     
       19. A composition according to  claim 17 , wherein said pyrazolotetrazoles of formula (Ic) are chosen from those compounds in which: 
       R 1  is a hydrogen atom or a methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano radical; and  
       R 2  is a hydrogen atom.  
     
     
       20. A composition according to  claim 17 , wherein said pyrazolo[1,5-a]imidazoles of formula (Id) are chosen from those compounds in which: 
       R 1  is a hydrogen atom or a methyl, trifluoromethyl, carboxyl, phenyl, ethoxy, cyano, amino, ethylthio or hydroxyl radical;  
       R 2  is a hydrogen atom; and  
       R 3  and R 4  are respectively a hydrogen atom and a hydrogen atom, a hydrogen atom and a methyl radical, a methyl radical and a hydrogen atom, a hydrogen atom and a phenyl radical, or a hydroxyl radical and a hydrogen atom; or R 3  and R 4  jointly form a phenyl ring.  
     
     
       21. A composition according to  claim 17 , wherein said pyrazolo[5,1-e]pyrazoles of formula (Ie) are chosen from those compounds in which: 
       R 1  is a hydrogen atom or a methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano radical;  
       R 2  is a hydrogen atom; and  
       R 3  and R 4  respectively are a hydrogen atom and a methyl radical, a methyl radical and a hydrogen atom, a methyl radical and a methyl radical, a hydrogen atom and a phenyl radical, or a hydrogen atom and an amino radical.  
     
     
       22. A composition according to  claim 17 , wherein said pyrazolo[5,1-e]-1,2,3-triazoles of formula (If) are chosen from those compounds in which: 
       R 1  is a hydrogen atom or a methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano radical;  
       R 2  is a hydrogen atom; and  
       R 3  is a hydrogen atom or a methyl radical.  
     
     
       23. A composition according to  claim 1 , wherein said at least one compound of formula (I) is chosen from: 
       7-amino-2-methylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-methyl-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-methyl-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-methyl-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-carboxy-2-methylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-carboxy-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-carboxy-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-carboxy-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-phenyl-2-methylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-phenyl-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-phenyl-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;  
       6,7-diamino-2-methylpyrazolo[1,5-b]-1,2,4-triazole;  
       6,7-diamino-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;  
       6,7-diamino-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;  
       6,7-diamino-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethylthio-2-methylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethylthio-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethylthio-2-isopropylpyrazolo[1,5-b]-2,4-triazole;  
       7-amino-6-ethylthio-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethoxy-2-methylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethoxy-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethoxy-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethoxy-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-methyl-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-carboxy-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-phenyl-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethylthio-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-methyl-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethylthio-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-carboxy-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-phenyl-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       6,7-diamino-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       6,7-diamino-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethoxy-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethoxy-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-3-methylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-methyl-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-methyl-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-methyl-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-methyl-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-methyl-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-methyl-3-(methylthio)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-phenyl-3-methylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-phenyl-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-phenyl-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-phenyl-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-phenyl-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-phenyl-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-phenyl-3-(methylthio)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethylthio-3-methylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethylthio-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethylthio-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethylthio-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethylthio-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethylthio-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-trifluoromethyl-3-(methylthio)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-(trifluoromethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-carboxy-3-methylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-carboxy-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-carboxy-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-carboxy-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-carboxy-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-carboxy-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       6,7-diamino-3-methylpyrazolo[3,2-c]-1,2,4-triazole;  
       6,7-diamino-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;  
       6,7-diamino-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;  
       6,7-diamino-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethoxy-3-methylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethoxy-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethoxy-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethoxy-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethoxy-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethoxy-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       6,7-diamino-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       6,7-diamino-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-methylpyrazolo[5,1-e]tetrazole;  
       7-amino-6-phenylpyrazolo[5,1-e]tetrazole;  
       7-amino-6-carboxypyrazolo[5,1-e]tetrazole;  
       7-amino-2-methylpyrazolo[1,5-a]imidazole;  
       7-amino-2-phenylpyrazolo[1,5-a]imidazole;  
       7-aminopyrazolo[1,5-a]benzimidazole;  
       7-amino-6-methylpyrazolo[1,5-a]imidazole;  
       7-amino-2,6-dimethylpyrazolo[1,5-a]imidazole;  
       7-amino-6-methyl-2-phenylpyrazolo[1,5-a]imidazole;  
       7-amino-6-methylpyrazolo[1,5-a]benzimidazole;  
       7-amino-6-phenylpyrazolo[1,5-a]imidazole;  
       7-amino-6-phenyl-2-methylpyrazolo[1,5-a]imidazole;  
       7-amino-2,6-diphenylpyrazolo[1,5-a]imidazole;  
       7-amino-6-phenylpyrazolo[1,5-a]benzimidazole;  
       7-amino-6-carboxypyrazolo[1,5-a]imidazole;  
       7-amino-6-carboxy-2-methylpyrazolo[1,5-a]imidazole;  
       7-amino-6-carboxy-2-phenylpyrazolo[1,5-a]imidazole;  
       7-amino-6-carboxypyrazolo[1,5-a]benzimidazole;  
       7-amino-6-ethoxypyrazolo[1,5-a]imidazole;  
       7-amino-6-ethoxy-2-methylpyrazolo[1,5-a]imidazole;  
       7-amino-6-ethoxy-2-phenylpyrazolo[1,5-a]imidazole;  
       7-amino-6-ethoxypyrazolo[1,5-a]benzimidazole;  
       7-amino-6-(trifluoromethyl)pyrazolo[1,5-a]benzimidazole;  
       7-amino-6-aminopyrazolo[1,5-a]imidazole;  
       7-amino-6-amino-2-methylpyrazolo[1,5-a]imidazole;  
       7-amino-6-amino-2-phenylpyrazolo[1,5-a]imidazole;  
       7-amino-6-aminopyrazolo[1,5-a]benzimidazole;  
       7-amino-6-(ethylthio)pyrazolo[1,5-a]imidazole;  
       7-amino-6-ethylthio-2-methylpyrazolo[1,5-a]imidazole;  
       7-amino-6-ethylthio-2-phenylpyrazolo[1,5-a]imidazole;  
       7-amino-6-methyl-2-hydroxypyrazolo[1,5-a]imidazole;  
       7-amino-6-phenyl-2-hydroxypyrazolo[1,5-a]imidazole;  
       7-amino-6-ethoxy-2-hydroxypyrazolo[1,5-a]imidazole;  
       7-amino-6-ethylthio-2-hydroxypyrazolo[1,5-a]imidazole;  
       6,7-diamino-2-hydroxypyrazolo[1,5-a]imidazole;  
       5,8-diamino-4-methylpyrazolo[5,1-e]pyrazole;  
       5,7,8-triamino-4-methylpyrazolo[5,1-e]pyrazole;  
       6-amino-5-methylpyrazolo[5,1-e]-1,2,3-triazole;  
       6-amino-5-phenylpyrazolo[5,1-e]-1,2,3-triazole;  
       and the acid addition salts thereof. 
     
     
       24. A composition according to  claim 17 , wherein said pyrazolo[1,5-b]-1,2,4-triazoles of formula (Ia) are chosen from: 
       7-amino-2-methylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-methyl-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-methyl-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-methyl-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-carboxy-2-methylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-carboxy-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-carboxy-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-carboxy-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-phenyl-2-methylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-phenyl-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-phenyl-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;  
       6,7-diamino-2-methylpyrazolo[1,5-b]-1,2,4-triazole;  
       6,7-diamino-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;  
       6,7-diamino-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;  
       6,7-diamino-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethylthio-2-methylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethylthio-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethylthio-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethylthio-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethoxy-2-methylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethoxy-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethoxy-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethoxy-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-methyl-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-carboxy-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-phenyl-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethylthio-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-methyl-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethylthio-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-carboxy-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-phenyl-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       6,7-diamino-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       6,7-diamino-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethoxy-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       7-amino-6-ethoxy-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;  
       and the acid addition salts thereof. 
     
     
       25. A composition according to  claim 17 , wherein said pyrazolo[3,2-c]-1,2,4-triazoles of formula (Ib) are chosen from: 
       7-amino-3-methylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-3-ethylpyrazolo[3,2-c-]1,2,4-triazole;  
       7-amino-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-methyl-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-methyl-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-methyl-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-methyl-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-methyl-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-methyl-3-(methylthio)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-phenyl-3-methylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-phenyl-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-phenyl-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-phenyl-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-phenyl-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-phenyl-3-(2′-phydroxyethy)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-phenyl-3-(methylthio)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethylthio-3-methylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethylthio-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethylthio-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethylthio-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethylthio-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethylthio-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-trifluoromethyl-3-(methylthio)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-(trifluoromethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-carboxy-3-methylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-carboxy-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-carboxy-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-carboxy-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-carboxy-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-carboxy-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       6,7-diamino-3-methylpyrazolo[3,2-c]-1,2,4-triazole;  
       6,7-diamino-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;  
       6,7-diamino-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;  
       6,7-diamino-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethoxy-3-methylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethoxy-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethoxy-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethoxy-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethoxy-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       7-amino-6-ethoxy-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       6,7-diamino-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       6,7-diamino-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;  
       and the acid addition salts thereof. 
     
     
       26. A composition according to  claim 17 , wherein said pyrazolotetrazoles of formula (Ic) are chosen from: 
       7-amino-6-methylpyrazolo[5,1-e]tetrazole;  
       7-amino-6-phenylpyrazolo[5,1-e]tetrazole;  
       7-amino-6-carboxypyrazolo[5,1-e]tetrazole;  
       and the acid addition salts thereof. 
     
     
       27. A composition according to  claim 17 , wherein said pyrazolo[1,5-a]imidazoles of formula (Id) are chosen from: 
       7-amino-2-methylpyrazolo[1,5-a]imidazole;  
       7-amino-2-phenylpyrazolo[1,5-a]imidazole;  
       7-aminopyrazolo[1,5-a]benzimidazole;  
       7-amino-6-methylpyrazolo[1,5-a]imidazole;  
       7-amino-2,6-dimethylpyrazolo[1,5-a]imidazole;  
       7-amino-6-methyl-2-phenylpyrazolo[1,5-a]imidazole;  
       7-amino-6-methylpyrazolo[1,5-a]benzimidazole;  
       7-amino-6-phenylpyrazolo[1,5-a]imidazole;  
       7-amino-6-phenyl-2-methylpyrazolo[1,5-a]imidazole;  
       7-amino-2,6-diphenylpyrazolo[1,5-a]imidazole;  
       7-amino-6-phenylpyrazolo[1,5-a]benzimidazole;  
       7-amino-6-carboxypyrazolo[1,5-a]imidazole;  
       7-amino-6-carboxy-2-methylpyrazolo[1,5-a]imidazole;  
       7-amino-6-carboxy-2-phenylpyrazolo[1,5-a]imidazole;  
       7-amino-6-carboxypyrazolo[1,5-a]benzimidazole;  
       7-amino-6-ethoxypyrazolo[1,5-a]imidazole;  
       7-amino-6-ethoxy-2-methylpyrazolo[1,5-a]imidazole;  
       7-amino-6-ethoxy-2-phenylpyrazolo[1,5-a]imidazole;  
       7-amino-6-ethoxypyrazolo[1,5-a]benzimidazole;  
       7-amino-6-(trifluoromethyl)pyrazolo[1,5-a]benzimidazole;  
       7-amino-6-aminopyrazolo[1,5-a]imidazole;  
       7-amino-6-amino-2-methylpyrazolo[1,5-a]imidazole;  
       7-amino-6-amino-2-phenylpyrazolo[1,5-a]imidazole;  
       7-amino-6-aminopyrazolo[1,5-a]benzimidazole;  
       7-amino-6-(ethylthio)pyrazolo[1,5-a]imidazole;  
       7-amino-6-ethylthio-2-methylpyrazolo[1,5-a]imidazole;  
       7-amino-6-ethylthio-2-phenylpyrazolo[1,5-a]imidazole;  
       7-amino-6-methyl-2-hydroxypyrazolo[1,5-a]imidazole;  
       7-amino-6-phenyl-2-hydroxypyrazolo[1,5-a]imidazole;  
       7-amino-6-ethoxy-2-hydroxypyrazolo[1,5-a]imidazole;  
       7-amino-6-ethylthio-2-hydroxypyrazolo[1,5-a]imidazole;  
       6,7-diamino-2-hydroxypyrazolo[1,5-a]imidazole;  
       and the acid addition salts thereof. 
     
     
       28. A composition according to  claim 17 , wherein said pyrazolo[5,1-e]pyrazoles of formula (Ie) are chosen from: 
       5,8-diamino-4-methylpyrazolo[5,1-e]pyrazole;  
       5,7,8-triamino-4-methylpyrazolo[5,1-e]pyrazole;  
       and the acid addition salts thereof. 
     
     
       29. A composition according to  claim 17 , wherein said pyrazolo[5,1-e]-1,2,3-triazoles of formula (If) are chosen from: 
       6-amino-5-methylpyrazolo[5,1-e]-1,2,3-triazole;  
       6-amino-5-phenylpyrazolo[5,1-e]-1,2,3-triazole;  
       and the acid addition salts thereof. 
     
     
       30. A composition according to  claim 1 , wherein said at least one compound of formula (I) is present in an amount ranging from 0.0005 to 12% by weight relative to the total weight of said composition. 
     
     
       31. A composition according to  claim 30 , wherein said at least one compound of formula (I) is present in an amount ranging from 0.005 to 6% by weight relative to the total weight of said composition. 
     
     
       32. A composition according to  claim 1 , wherein said medium suitable for dyeing comprises water, a water/alcohol mixture or a mixture of water and of at least one organic solvent. 
     
     
       33. A composition according to  claim 32 , wherein said at least one organic solvent is a C 1 -C 4  lower alkanol, a glycerol, a glycol, a glycol ether, an aromatic alcohol, or a mixture thereof. 
     
     
       34. A composition according to  claim 32 , wherein said at least one organic solvent represents from 1 to 40% by weight relative to the total weight of said composition. 
     
     
       35. A composition according to  claim 1 , wherein said composition has a pH ranging from 3 to 12. 
     
     
       36. A composition according to  claim 35 , wherein said composition has a pH ranging from 5 to 11. 
     
     
       37. A composition according to  claim 1 , wherein said composition further contains at least one coupler. 
     
     
       38. A composition according to  claim 37 , wherein said at least one coupler is chosen from an aromatic diamine, a meta-aminophenol, a meta-diphenol and a heterocyclic coupler. 
     
     
       39. A composition according to  claim 37 , wherein said at least one coupler is chosen from 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxy-benzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-amino-4-(β-hydroxyethyl)amino-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)-propane, sesamol, α-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole, 6-methylpyrazolo-[1,5-a]benzimidazole, and the acid addition salts thereof. 
     
     
       40. A composition according to  claim 37 , wherein said at least one coupler is present in an amount ranging from 0.0001 to 10% by weight relative to the total weight of said composition. 
     
     
       41. A composition according to  claim 40 , wherein said at least one coupler is present in an amount ranging from 0.005 to 5% by weight relative to the total weight of said composition. 
     
     
       42. A composition according to  claim 1 , wherein said composition further comprises at least one additional oxidation base. 
     
     
       43. A composition according to  claim 42 , wherein said at least one additional oxidation base is chosen from a para-phenylenediamine, a bisphenylalkylenediamine, a para-aminophenol, an ortho-aminophenol and a heterocyclic base other than said pyrazoloazole compounds of formula (I). 
     
     
       44. A composition according to  claim 42 , wherein said at least one additional oxidation base is present in an amount ranging from 0.0005 to 12% by weight relative to the total weight of said composition. 
     
     
       45. A composition according to  claim 1 , wherein said at least one acid addition salt is a hydrochloride, a hydrobromide, a sulphate, a citrate, a succinate, a tartrate, a tosylate, a benzenesulphonate, a lactate or an acetate. 
     
     
       46. A composition according to  claim 1 , wherein said composition additionally contains at least one direct dye. 
     
     
       47. A method for dyeing keratinous fibers comprising contacting said fibers with at least one oxidation dye composition according to  claim 1 , in the presence of air or an oxidizing agent, for a time sufficient to achieve color development. 
     
     
       48. The method according to  claim 47 , wherein said keratinous fibers are human keratinous fibers. 
     
     
       49. The method according to  claim 48 , wherein said human keratinous fibers are hair. 
     
     
       50. A method according to  claim 47 , wherein said color development is achieved without an oxidizing agent, but with contact only with atmospheric oxygen. 
     
     
       51. The method according to  claim 47 , wherein said dye composition is mixed at the time of use with an oxidizing composition comprising, in a medium suitable for dyeing, at least one oxidizing agent present in an amount sufficient for color development. 
     
     
       52. The method according to  claim 47 , wherein said dye composition additionally contains at least one oxidation catalyst. 
     
     
       53. The method according to  claim 52 , wherein said at least one oxidation catalyst is a metal salt. 
     
     
       54. The method according to  claim 53 , wherein said metal salt is manganese, cobalt, copper, iron, silver or zinc. 
     
     
       55. The method according to  claim 53 , wherein said metal salt is manganese diacetate tetrahydrate, manganese dichloride, manganese triacetate or a hydrate thereof, manganese trichloride, zinc dichloride, zinc diacetate dihydrate, zinc carbonate, zinc dinitrate, zinc sulphate, iron dichloride, iron sulphate, iron diacetate, cobalt diacetate tetrahydrate, cobalt carbonate, cobalt dichloride, cobalt sulphate heptahydrate, cupric chloride or ammoniacal silver nitrate. 
     
     
       56. The method according to  claim 53 , wherein said metal salt is present in an amount ranging from 0.001 to 4% by weight relative to the total weight of said dye composition. 
     
     
       57. The method according to  claim 56 , wherein said metal salt is present in an amount ranging from 0.005 to 2% by weight relative to the total weight of said dye composition. 
     
     
       58. The method according to  claim 51 , wherein said at least one oxidizing agent is hydrogen peroxide, urea hydrogen peroxide, an alkali metal bromate, a persalt, or an enzyme. 
     
     
       59. The method according to  claim 58 , wherein said persalt is a perborate or a persulphate. 
     
     
       60. The method according to  claim 58 , wherein said enzyme is a peroxidase or an oxidoreductase with 2 unpaired electrons. 
     
     
       61. The method according to  claim 47 , wherein said color is developed at acidic, neutral, or alkaline pH with an oxidizing agent which is added to said oxidation dyeing composition at the time of application or which is present in an oxidizing composition that is applied: 
       (i) separately from the dye composition at the same time that said dye composition is applied to said fibers, or  
       (ii) sequentially with the dye composition.  
     
     
       62. The method according to  claim 47 , wherein said time ranges from 3 to 50 minutes. 
     
     
       63. The method according to  claim 62 , wherein said time ranges from 5 to 30 minutes. 
     
     
       64. The method according to  claim 51 , wherein said oxidizing composition has a pH ranging from 3 to 12. 
     
     
       65. The method according to  claim 64 , wherein said oxidizing composition has a pH ranging from 5 to 11. 
     
     
       66. The composition according to  claim 1 , said composition being in the form of a liquid, a cream, a gel or any other form suitable for dyeing keratinous fibers. 
     
     
       67. A multi-compartment dyeing device or kit for dyeing keratin fibers, comprising at least two compartments, 
       a first compartment of which contains a dyeing composition according to  claim 1  and  
       a second compartment of which contains an oxidizing composition.